Transition Metal-Substituted Diphosphenes. 34. Studies on the Reactivity of Metallodiphosphenes (.eta.5-C5R5)(CO)2M-P:P-Mes* of Iron and Ruthenium toward Hexafluoroacetone. X-ray Structure Analyses of (.eta.5-C5Me5)(CO)M-P(:PMes*)OC(CF3)2C(O) (M = Fe, Ru), (.eta.5-1,2,4-iPr3C5H2)(CO)Ru-P(:PMes*)OC(CF3)2C(O), and (.eta.5-C5Me5)(CO)2Fe-P-P(Mes*)OC(CF3)2

Weber, Lothar; Misiak, Hanns; Buchwald, Susanne; Stammler, Hans‐Georg; Neumann, Beate

doi:10.1021/om00018a012

Cited by 10 publications

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Reactions of Phosphaalkenes with Hexafluoroacetone

et al. 1995

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The dimethylamino-substituted phosphaalkene 1 reacts with hexafluoroacetone (HFA) with addition at the P=C bond to form the 1,5,2-dioxaphosphorinane 2. The structure of 2 was confirmed by an X-ray crystal structure analysis. The sixmembered ring displays an envelope conformation with the phosphorus atom out of the plane, but the phosphorus is disordered over two sites. Reaction of P-trimethylsilyl-substituted phosphaalkenes with HFA proceeds with retention of the P=C double bond and insertion of HFA into the P-Si bond. Two isomeric products are obtained and are characterized by IH-, I3C-, 19F-, and 31P-NMR spectroscopy, IR spectroscopy, mass spectrometry, and elemental analysis.The reactivity of h4-phosphorus double bond systems ->P=E-R (E = N, P; R = hydrocarbon group) towards HFA has been intensively studied [']. Compounds of phosphorus in low coordination number, e.g. iminophosphanes, are converted by HFA either to h4-oxaphosphiranes AL2] ([2 + 11 cycloaddition) or to 1,3,2-0xazaphosphetanes BL3] ([2 + 21 cycloaddition), depending on the substituents RI and R2 (Scheme 1).

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